Elastomer formulations comprising discrete carbon nanotube fibers

ABSTRACT

This present invention relates to the carbon nanotubes as composites with materials such as elastomers, thermosets and thermoplastics. A further feature of this invention relates to the development of a concentrate of carbon nanotubes with an elastomer wherein the concentrate can be further diluted with an elastomer and other polymers and fillers using conventional melt mixing equipment.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 13/993,206 filedJun. 11, 2013 claiming priority to PCT/EP2011/072427 filed Dec. 12, 2011which claimed priority from U.S. provisional application 61/423,033.

FIELD OF INVENTION

The present invention is directed to novel compositions and methods forproducing elastomer composite blends with discrete carbon nanotubes.

BACKGROUND OF THE INVENTION

Carbon nanotubes can be classified by the number of walls in the tube,single-wall, double wall and multiwall. Each wall of a carbon nanotubecan be further classified into chiral or non-chiral forms. Carbonnanotubes are currently manufactured as agglomerated nanotube balls orbundles. Use of carbon nanotubes as a reinforcing agent in polymercomposites is an area in which carbon nanotubes are predicted to havesignificant utility. However, utilization of carbon nanotubes in theseapplications has been hampered due to the general inability to reliablyproduce individualized carbon nanotubes. To reach the full potential ofperformance enhancement of carbon nanotubes as composites in polymersthe aspect ratio, that is length to diameter ratio, should besubstantially greater than 40. The maximum aspect ratio for a given tubelength is reached when each tube is fully separated from another. Abundle of carbon nanotubes, for example, has an effective aspect ratioin composites of the average length of the bundle divided by the bundlediameter.

Various methods have been developed to debundle or disentangle carbonnanotubes in solution. For example, carbon nanotubes may be shortenedextensively by aggressive oxidative means and then dispersed asindividual nanotubes in dilute solution. These tubes have low aspectratios not suitable for high strength composite materials. Carbonnanotubes may also be dispersed in very dilute solution as individualsby sonication in the presence of a surfactant. Illustrative surfactantsused for dispersing carbon nanotubes in aqueous solution include, forexample, sodium dodecyl sulfate, or cetyltrimethyl ammonium bromide. Insome instances, solutions of individualized carbon nanotubes may beprepared from polymer-wrapped carbon nanotubes. Individualizedsingle-wall carbon nanotube solutions have also been prepared in verydilute solutions using polysaccharides, polypeptides, water-solublepolymers, nucleic acids, DNA, polynucleotides, polyimides, andpolyvinylpyrrolidone. The dilution ranges are often in the mg/literranges and not suitable for commercial usage.

SUMMARY OF THE INVENTION

The present invention relates to a composition comprising a plurality ofdiscrete carbon nanotube fibers having an aspect ratio of from about 25to about 500, and at least one natural or synthetic elastomer, andoptionally at least one filler. The composition can have carbon nanotubefibers with an oxidation level of from about 3 weight percent to about15 weight percent. The carbon nanotube fibers comprise preferably ofabout 1 weight percent to about 30 weight percent of the composition andthe composition is in the form of free flowing particles or a bale. Thecomposition is further comprising of at least one surfactant ordispersing aid. The composition can comprise the natural or syntheticelastomer selected from the group consisting of, but not limited to,natural rubbers, polyisobutylene, polybutadiene and styrene-butadienerubber, butyl rubber, polyisoprene, styrene-isoprene rubbers,styrene-isoprene rubbers, ethylene propylene diene rubbers, silicones,polyurethanes, polyester-polyethers, hydrogenated and non-hydrogenatednitrile rubbers, halogen modified elastomers, flouro-elastomers, andcombinations thereof. The composition contains fibers that are notentangled as a mass and are uniformly dispersed in the elastomer.

In another embodiment, the invention is a process to form a carbonnanotube fiber/elastomer composite comprising the steps of: (a)selecting discrete carbon nanotube fibers having an aspect ratio of from25 to 500, (b) blending the fibers with a liquid to form a liquid/fibermixture, (c) optionally adjusting the pH to a desired level, (d)agitating the mixture to a degree sufficient to disperse the fibers toform a dispersed fiber mixture, (e) optionally combining the dispersedfiber mixture with at least one surfactant, (f) combining the dispersedfiber mixture with at least one elastomer at a temperature sufficient toincorporate the dispersed fiber mixture to form a carbon nanotubefiber/elastomer composite/liquid mixture, (g) isolating the resultingcarbon nanotube fiber/elastomer composite from the liquid. The carbonnanotube fibers comprise from about 1 to about 30 weight percent of thefiber/elastomer composite of (g). The liquid is aqueous based. Theagitating step (d) comprises sonication. In this embodiment, theelastomer is selected from, but not limited to, the natural or syntheticelastomer selected from the group consisting of, but not limited to,natural rubbers, polyisobutylene, polybutadiene and styrene-butadienerubber, butyl rubber, polyisoprene, styrene-isoprene rubbers,styrene-isoprene rubbers, ethylene propylene diene rubbers, silicones,polyurethanes, polyester-polyethers, hydrogenated and non-hydrogenatednitrile rubbers, halogen modified elastomers, fluoro-elastomers, andcombinations thereof. The composition is further comprising sufficientnatural or synthetic elastomer to form a formulation comprising fromabout 0.1 to about 25 weight percent carbon nanotube fibers.

In another embodiment, the invention is a formulation in the form of amolded or fabricated article, such as a tire, a hose, a belt, a seal anda tank track pad, wheel, bushings or backer plate components.

In another embodiment, the invention is a nanotubes/elastomer compositefurther comprising of filler or fillers such as carbon black and/orsilica, and wherein a molded film comprising the composition has atensile modulus at 5 percent strain of at least about 12 MPa. Thecomposition comprising of carbon black, and wherein a molded filmcomprising the composition has a tear property of at least about 0.8MPa.

In yet another embodiment of the invention is a carbonnanotube/elastomer composition further comprising of filler, and wherein a molded film comprising the composition has a tensile modulus at 5%strain of at least 8 MPa.

In yet another embodiment of the invention is a carbon nanotubefiber/elastomer composite, wherein the carbon nanotube fibers arediscrete fibers and comprise from about 10 to about 20 weight percentfibers and wherein the elastomer comprises a styrene copolymer rubber.

In still another embodiment of the invention is a method for obtainingindividually dispersed carbon nanotubes in rubbers and/or elastomerscomprising (a) forming a solution of exfoliated carbon nanotubes at pHgreater than or equal to about 7, (b) adding the solution to a rubber orelastomer latex to form a mixture at pH greater than or equal to about7, (c) coagulating the mixture to form a concentrate, (d) optionallyincorporating other fillers into the concentrate, and (e) melt-mixingsaid concentrate into rubbers and/or elastomers to form elastomericcomposites. In this embodiment the carbon nanotubes comprise less thanor equal to about 2 percent by weight of the solution. A furtherembodiment is that the coagulation step comprises mixing with acetone.In another embodiment, the coagulation step comprises drying themixture. In yet another embodiment the coagulation step comprises addingat least one acid to the mixture at pH less than or equal to about 4.5together with at least one monovalent inorganic salt. In anotherembodiment, the mixture has divalent or multivalent metal ion content ofless than about 20,000 parts per million, preferably less than about10,000 parts per million and most preferably less than about 1,000 partsper million.

Another aspect of this invention are coagulating methods/agents arethose that enable the carbon nanotube to be non-ordered on the surfaceof the elastomer latex particle and together are substantially removablefrom the liquid mixture. A further aspect of this invention is a methodto reduce or remove surfactants in the latex/carbon nanotube fibercomposite system organic molecules of high water solubility such asacetone, denatured alcohol, ethyl alcohol, methanol, acetic acid,tetrahydrofuran. Another aspect of this invention is to selectcoagulating methods that retain surfactant in the latex/carbon nanotubefiber material which includes coagulating methods such as sulfuric acidand inorganic monovalent element salt mixtures, acetic acid andmonovalent element salt mixtures, formic acid and inorganic monovalentelement salt mixtures, air drying, air spraying, steam stripping andhigh speed mechanical agitation.

Yet another embodiment of the invention is an individually dispersedcarbon nanotube/rubber or carbon nanotube/elastomer concentratecomprising free flowing particles or a bale. A further aspect of thisinvention is an individually dispersed carbon nanotube/rubber or carbonnanotube/elastomer concentrate comprising free flowing particles or abale wherein the concentrate contains a concentration of less than20,000 parts per million of divalent or multivalent metal salt.

Another embodiment of the invention is an individually dispersed carbonnanotube/rubber or carbon nanotube/elastomer concentrate comprising freeflowing particles or a bale wherein the concentrate containsagglomerations of carbon nanotubes that comprise less than 1 percent byweight of the concentrate and wherein the carbon nanotube agglomeratescomprise more than 10 microns in diameter. An embodiment of theinvention is a composite comprising the concentrate.

In another embodiment, the elastomer nanotube fiber composition,particularly materials made from elastomers commonly called eithernatural or synthetic rubber or rubber compounds (with the addition offillers such as carbon or silicon) includes wherein the fiber surfacemodifier or surfactant is chemically or physically (or both) bonded tothe elastomer and/or the isolated fibers or the filler in the compounds.

In another embodiment, the material-nanotube fiber composition includeswherein the fiber surface modifier or surfactant is chemically bonded tothe material and/or fiber. As an example, oleylamine(1-amino-9-octadecene) can be reacted with carbon nanotubes containingcarboxylic groups to give the amide. On addition of the amide modifiedcarbon nanotube fiber to a vinyl containing polymer material such asstyrene-butadiene followed by addition of crosslinking agents comprisingsuch as peroxides or sulfur, the vinyl containing polymer can becovalently bonded to the amide functionality of the carbon nanotube.

In one embodiment of this invention a method is disclosed in which theelastomer/carbon nanotube concentrate is dispersed first into anotherelastomer or thermoplastic to a uniform consistency before addition ofother additives such as other fillers and additives, including carbonblack, silica, graphene, oils and antioxidants.

Another embodiment of this invention is a method of mixing carbonnanotubes and at least one first elastomer, wherein a master batch ofcarbon nanotubes is first melt mixed with the elastomer, either the sameor different from the first elastomer, at a temperature from about 20 toabout 200° C., subsequently then additional elastomers, fillers, andadditives are added and melt mixed further, to produce a compositionsuitable for vulcanization. A solvent can be added to facilitate mixingwhich can be removed after the at least one first elastomer, wherein amaster batch of carbon nanotubes is first mixed with the elastomer, orafter all ingredient are added and mixed.

The exfoliated carbon nanotube fibers of this invention impartsignificant strength and stiffness to the materials. These new elastomernanotube filler materials can improve the frictional, adhesive,cohesive, noise and vibration, rolling resistance, tear, wear, fatigueand crack resistance, hysteresis, large strain effects (Mullins effect),small strain effects (Payne effect) and oscillation or frequencyproperties and swelling resistance to oil of the elastomers andelastomer compounds. This change in properties will be beneficial forapplications such as tires or other fabricated rubber or rubbercompounded parts.

For a more complete understanding of the present disclosure, and theadvantages thereof, reference is now made to the following descriptionsdescribing specific embodiments of the disclosure.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, certain details are set forth such asspecific quantities, sizes, etc., so as to provide a thoroughunderstanding of the present embodiments disclosed herein. However, itwill be evident to those of ordinary skill in the art that the presentdisclosure may be practiced without such specific details. In manycases, details concerning such considerations and the like have beenomitted inasmuch as such details are not necessary to obtain a completeunderstanding of the present disclosure and are within the skills ofpersons of ordinary skill in the relevant art.

While most of the terms used herein will be recognizable to those ofordinary skill in the art, it should be understood, however, that whennot explicitly defined, terms should be interpreted as adopting ameaning presently accepted by those of ordinary skill in the art. Incases where the construction of a term would render it meaningless oressentially meaningless, the definition should be taken from Webster'sDictionary, 3rd Edition, 2009. Definitions and/or interpretations shouldnot be incorporated from other patent applications, patents, orpublications, related or not, unless specifically stated in thisspecification or if the incorporation is necessary for maintainingvalidity.

Functionalized carbon nanotubes of the present disclosure generallyrefer to the chemical modification of any of the carbon nanotube typesdescribed hereinabove. Such modifications can involve the nanotube ends,sidewalls, or both. Chemical modifications may include, but are notlimited to covalent bonding, ionic bonding, chemisorption,intercalation, surfactant interactions, polymer wrapping, cutting,solvation, and combinations thereof. In some embodiments, the carbonnanotubes may be functionalized before, during and after beingexfoliated.

In various embodiments, a plurality of carbon nanotubes is disclosedcomprising single wall, double wall or multi wall carbon nanotube fibershaving an aspect ratio of from about 25 to about 500, preferably fromabout 60 to about 200, and a oxidation level of from about 3 weightpercent to about 15 weight percent, preferably from about 5 weightpercent to about 10 weight percent. The oxidation level is defined asthe amount by weight of oxygenated species covalently bound to thecarbon nanotube. The thermogravimetric method for the determination ofthe percent weight of oxygenated species on the carbon nanotube involvestaking about 5 mg of the dried oxidized carbon nanotube and heating at5° C./minute from room temperature to 1000 degrees centigrade in a drynitrogen atmosphere. The percentage weight loss from 200 to 600 degreescentigrade is taken as the percent weight loss of oxygenated species.The oxygenated species can also be quantified using fourier transforminfra-red spectroscopy, FTIR, particularly in the wavelength range1730-1680 cm⁻¹.

The carbon nanotube fibers can have oxidation species comprising ofcarboxylic acid or derivative carbonyl containing species and areessentially discrete individual fibers, not entangled as a mass. Thederivative carbonyl species can include ketones, quaternary amines,amides, esters, acyl halogens, monovalent metal salts and the like.

As-made carbon nanotubes using metal catalysts such as iron, aluminum orcobalt can retain a significant amount of the catalyst associated orentrapped within the carbon nanotube, as much as five weight percent ormore. These residual metals can be deleterious in such applications aselectronic devices because of enhanced corrosion or can interfere withthe vulcanization process in curing elastomer composites. Furthermore,these divalent or multivalent metal ions can associate with carboxylicacid groups on the carbon nanotube and interfere with the discretizationof the carbon nanotubes in subsequent dispersion processes. In otherembodiments, the oxidized fibers comprise a residual metal concentrationof less than about 10000 parts per million, ppm, and preferably lessthan about 1000 parts per million. The metals can be convenientlydetermined using energy dispersive X-ray, EDX.

In another embodiment, a mixture of master batches using differentrubbers added to blends of different rubbers used in the rubber compoundsuch that each rubber has a master batch that is compatible so that theindividually dispersed nanotubes are distributed whether uniformly ornon-uniformly in each rubber domain. This is sometimes necessary so thatblends of rubbers used in the rubber compound will have carbon nanotubesin each rubber component.

An illustrative process for producing discrete oxidized carbon nanotubesfollows: 3 liters of sulfuric acid, 97 percent sulfuric acid and 3percent water, and 1 liter of concentrated nitric acid containing 70percent nitric acid and 3 percent water, are added into a 10 litertemperature controlled reaction vessel fitted with a sonicator andstirrer. 40 grams of non-discrete carbon nanotubes, grade Flowtube 9000from CNano corporation, are loaded into the reactor vessel whilestirring the acid mixture and the temperature maintained at 30° C. Thesonicator power is set at 130-150 watts and the reaction is continuedfor three hours. After 3 hours the viscous solution is transferred to afilter with a 5 micron filter mesh and much of the acid mixture removedby filtering using a 100 psi pressure. The filter cake is washed onetimes with four liters of deionized water followed by one wash of fourliters of an ammonium hydroxide solution at pH greater than 9 and thentwo more washes with four liters of deionized water. The resultant pH ofthe final wash is 4.5. A small sample of the filter cake is dried invacuum at 100° C. for four hours and a thermogravimetric analysis takenas described previously. The amount of oxidized species on the fiber is8 percent weight and the average aspect ratio as determined by scanningelectron microscopy to be 60.

The discrete oxidized carbon nanotubes (CNT) in wet form are added towater to form a concentration by weight of 1 percent and the pH isadjusted to 9 using ammonium hydroxide. Sodium dodecylbenzene sulfonicacid and is added at a concentration 1.25 times the mass of oxidizedcarbon nanotubes. The solution is sonicated while stirring until the CNTare fully dispersed in the solution. Full dispersion of individual tubesis defined when the UV absorption at 500 nm is above 1.2 absorptionunits for a concentration of 2.5×10⁻⁵ g CNT/ml. Latex SBR LPF 5356(Goodyear Rubber Company) with a solids SBR concentration of 70.2% (byweight) was added to the CNT solution such that the solids ratio is 10parts CNT for 90 parts SBR by weight.

Sulfuric acid is then added sufficient to bring the pH to 2 and sodiumchloride added at a ratio of 50 g/liter of fluid while stirring.Stirring continues for 10 minutes then the coagulant is removed byfiltering. The filtrate is a clear liquid. The coagulant is dried in avacuum oven at 40° C. overnight.

Preparation of the Vulcanizable Composition According to the PresentInvention:

A further object of the invention resides in the preparation of thevulcanizable compositions, wherein the elastomer, the concentrate ofcarbon-nanotubes in an elastomer composition and the cross-linking agentand optionally any of the other ingredients of the composition are mixedtogether. Typically the mixing is performed at an elevated temperaturethat may range from about 20° C. to about 200° C. The mixing may furtherbe performed in the presence of a solvent which is then removed aftermixing.

Normally the mixing time does not exceed one hour and a time in therange from 2 to 30 minutes is usually adequate.

The mixing is suitably carried out in a blending apparatus, e.g. aninternal mixer such as a Banbury mixer, or a Haake or Brabenderminiature internal mixer. A two roll mill mixer also provides a gooddispersion of the carbon-nanotubes as well as of the other optionaladditives within the elastomer. An extruder also provides good mixing,and permits shorter mixing times. It is possible to carry out the mixingin two of more stages, and the mixing can be done in differentapparatus, for example one stage in an internal mixer and one stage inan extruder. However, it should be taken care that no unwantedpre-crosslinking (=scorch) occurs during the mixing stage.

The compounding and vulcanization may be performed as known to anyartisan (see e.g. Encyclopedia of Polymer Science and Engineering, Vol.4, p. 66 et seq. (Compounding) and Vol. 17, p. 666 et seq.(Vulcanization)). Typically such vulcanization is performed at atemperature in the range of from 100 to 200° C., preferably 130 to 180°C. In one embodiment the preparation of a polymer vulcanizate comprisessubjecting the inventive composition to a vulcanization during injectionor extrusion molding.

Following is an example using styrene butadiene as an elastomer withaddition of carbon nanotubes of this invention.

EXAMPLE 1

The SBR concentrate is melt mixed with additional SBR (LanxessVSL-5052-OHM) to give a final CNT concentration of 2 percent weight in aBrabender mixer by the following procedure. The temperature of thebarrel is set to 115° C. The SBR and master batch is introduced into thebarrel at a speed of 20-30 rpm. The speed is then increased to 50 rpm.Barrel temperature should reach 125° C. When the torque has reached aconstant value, the speed is decreased to 5 rpm and the temperaturecontroller is turned off. When the temperature in the barrel is 95° C.,the speed is increased to 50 rpm. The cure package is added and mixingcontinues for 5 minutes. The cure package consists of sulfur 3.5 partsper hundred resin, phr, tetrabutylbenzothiozolsulfonamide 0.75 phr,diphenylguanidine 0.5 phr, stearic acid 1.5 phr, N-(1,3 Dimethylbutyl)N′-phenyl-p-phenyldiamine 2 phr and zinc oxide 3 phr.

A comparative 1 is made as above with the exception that no SBRconcentrate is added.

The mixture is then cured under the following procedure using acompression molder. The platten temperature is set to 160° C., thecuring overall time to 20 minutes and the water cooling time to 5minutes. A mass of 40.6 g of rubber sample is cut into small ¼″ piecesand placed in the center of mold window such that it forms a square,occupying ⅔ of the space. Foil sheets are used between sample andcompression plates. Mold release is only used on the mold frame. Thesample is compressed with pressure less than 10 psi for 2 minutes. Then,the pressure is increased to 25 tons and kept constant for the remainingcuring cycle.

After curing the films are tested in tension at 25° C. using a tensiletester with an initial strain rate of 1×10⁻² s⁻¹. Engineering Stress isthe load divided by the initial cross-sectional area of the specimen.Strain is defined as the distance traversed by the crosshead of theinstrument divided by the initial distance between the grips. The 100%modulus is that value of tensile stress at 100% strain. The films arealso tested for work done to completely tear the specimen by introducinga razor edge notch of dimension one half the width and perpendicular tothe length of the specimen to a tensile specimen.

TABLE 1 Tensile properties of cured SBR without carbon nanotubes (Comp.Ex. 1) and SBR with discrete carbon nanotubes (Ex. 1) Tensile Strength100% Modulus Work done to Tear Sample (MPa) (MPa) (MPa) Comparative 11.1 0.51 0.46 SBR Example 1 2.26 0.8 0.79 SBR + 2% wt CNT

Seen in Table 1, significant improvements in the values of tensilestrength, 100% modulus and work done to tear are gained using 2 percentweight of the carbon nanotubes of this invention. These attributes areimportant elements that will lead to improved wear in elastomercomposites.

In another aspect of this invention is a preferred method of mixing thatresults in improved properties wherein the master batch of carbonnanotubes is first melt mixed with another elastomer then additionalrubbers, fillers and additives are added and melt mixed further toproduce a composition suitable for vulcanization.

Following is an Example of Preferred Mixing

A comparative example 2 is produced using 3 phr carbon nanotubes of thisinvention, and carbon black filled rubber system consisting of 3 meltpasses. The first pass was to mix the rubber components 60 phr styrenebutadiene, SBR Lanxess VSL-5025-OHM and 40 phr Natural Rubber CB 60grade, and an SBR-carbon nanotubes master batch containing 10 weightpercent carbon nanotubes at about 160° C. The second pass was to mixinto the first pass products 50 phr carbon black, type N330, 5 phrprocessing oil Sundex 8125, 1 phr antioxidant 6 PPD Santoflex, 3 phrzinc oxide and 3 phr stearic acid at about 160° C. The third pass was tomix in the sulfur curing compounds 1.5 phr sulfur and 1.3 phr TBBS atabout 110° C. Each pass was performed with a fill factor of 75% using aBrabender mixer.

EXAMPLE 2

The improved mixing approach is the same as the control except the firstpass is mixing the SBR with the carbon nanotubes master batch for 5minutes at about 170° C. followed by adding the natural rubber at about160° C. and melt mixing for a further 5 minutes.

The results of testing the materials after curing for 8 minutes at about160° C. are provided in Table 2. The tear initiation and total tearenergy are determined from tear specimen ASTM D624-C.

TABLE 2 Comparative 2 Example 2 Tensile Stress at Break (MPa) 18.8 20.6Tensile Elongation to Break % 500 520 Tear Initiation Energy (MPa) 2.93.7 Total Tear Energy (MPa) 3.3 4.2

The above table 2 shows that the example of the invention (predilutedmaster batch with specific mixing) obtains improved tensile stress atbreak at over 1.7 MPa, improved tear initiation energy at over 0.7 MPaand including improved total tear energy at over 0.8 MPa versus thecomparative example comprising different mixing techniques, proving theutility and inventiveness of the compositions of the invention.

Embodiments

-   -   1. A composition comprising a plurality of discrete carbon        nanotube fibers having an aspect ratio of from about 25 to about        500, and at least one natural or synthetic elastomer, and        optionally at least one filler.    -   2. The composition of claim 1 wherein at least 70 percent,        preferably at least 80 percent, by weight of the nanotube fibers        are fully exfoliated.    -   3. The composition of claim 1 wherein the nanotube fibers are        further functionalized.    -   4. The composition of claim 1 wherein the carbon nanotube fibers        comprise an oxidation level from about 3 weight percent to about        15 weight percent.    -   5. The composition of claim 1 wherein the carbon nanotube fibers        comprise from about 1 weight percent to about 30 weight percent        of the composition.    -   6. The composition of claim 1 in the form of free flowing        particles.    -   7. The composition of claim 1 further comprising at least one        surfactant or dispersing aid.    -   8. The composition of claim 1 wherein the natural or synthetic        elastomer is selected from the group consisting of natural        rubbers, polyisobutylene, polybutadiene and styrene-butadiene,        butyl rubber, polyisoprene, ethylene propylene diene rubbers and        hydrogenated and non-hydrogenated nitrile rubbers,        polyurethanes, polyethers, silicones, halogen modified        elastomers, especially chloroprene and fluoroelastomers and        combinations thereof.    -   9. The composition of claim 1 wherein the fibers are not        entangled as a mass.    -   10. A process to form a carbon nanotube fiber/elastomer        composite comprising the steps of:        -   (a) selecting discrete carbon nanotube fibers having an            aspect ratio of from 25 to 500,        -   (b) blending the fibers with a liquid to form a liquid/fiber            mixture,        -   (c) optionally adjusting the pH to a desired level,        -   (d) agitating the mixture to a degree sufficient to disperse            the fibers to form a dispersed fiber mixture,        -   (e) optionally combining the dispersed fiber mixture with at            least one surfactant,        -   (f) combining the dispersed fiber mixture with at least one            elastomer at a temperature sufficient to incorporate the            dispersed fiber mixture to form a carbon nanotube            fiber/elastomer composite/liquid mixture,        -   (g) isolating the resulting carbon nanotube fiber/elastomer            composite from the liquid.    -   11. The process of claim 10 wherein the carbon nanotube fibers        comprise from about 1 to about 30 weight percent of the        fiber/elastomer composite of (g).    -   12. The process of claim 10 wherein the liquid is aqueous based.    -   13. The process of claim 10 wherein the agitating step (d)        comprises sonication.    -   14. The process of claim 10 wherein the elastomer is selected        from the group consisting of natural rubbers, polyisobutylene,        polybutadiene and styrene-butadiene rubber, ethylene propylene        diene rubbers, butyl rubber, polyisoprene and hydrogenated and        non-hydrogenated nitrile rubbers, polyurethanes, polyethers,        halogen containing elastomers and fluoroelastomers and        combinations thereof.    -   15. The composition of claim 1 further comprising sufficient        natural or synthetic elastomer to form a formulation comprising        from about 0.1 to about 25 weight percent carbon nanotube        fibers.    -   16. The composition of claim 1 in the form of a molded or        fabricated article, such as a tire, a hose, a belt, a seal and a        tank track.    -   17. The composition of claim 1 further comprising carbon black        and/or silica and wherein a molded film comprising the        composition has a tensile modulus at 5% strain and 25 degrees C.        of at least about 12 MPa.    -   18. The composition of claim 1 further comprising carbon black        and/or silica, and wherein a molded film comprising the        composition has a tear property at 25 degrees C. of at least        about 0.8 MPa.    -   19. The composition of claim 1 further comprising filler, and        wherein a molded film comprising the composition has a tensile        modulus at 5% strain and 25 degrees C. of at least about 8 MPa.    -   20. A carbon nanotube fiber/elastomer composite, wherein the        carbon nanotube fibers are discrete fibers and comprise from        about 10 to about 20 weight percent fibers and wherein the        elastomer comprises a styrene copolymer rubber.    -   21. A method for obtaining individually dispersed carbon        nanotubes in rubbers and/or elastomers comprising (a) forming a        solution of exfoliated carbon nanotubes at pH greater than or        equal to about 7, (b) adding the solution to a rubber or        elastomer latex to form a mixture at pH greater than or equal to        about 7, (c) coagulating the mixture to form a concentrate, (d)        optionally incorporating other fillers into the concentrate,        and (e) melt-mixing said concentrate into rubbers and/or        elastomers to form elastomeric composites.    -   22. The method of claim 21 wherein the carbon nanotubes comprise        less than or equal to about 2% wt of the solution.    -   23. The method of claim 21 wherein the coagulation step (c)        comprises mixing with organic molecules of high water solubility        such as acetone, denatured alcohol, ethyl alcohol, methanol,        acetic acid, tetrahydrofuran that partially or wholly removes        surfactants form the latex/carbon nanotube fiber concentrate.    -   24. The method of claim 21 wherein the coagulation step (c)        comprises drying, steam stripping or mechanical agitation of the        mixture to fully retain surfactants from the latex/carbon        nanotube fiber concentrate.    -   25. The method of claim 21 wherein the coagulation step (c)        comprises adding a polymeric coagulating agent, preferably        polyethylene oxide.    -   26. The method of claim 21 wherein the coagulation step (c)        comprises adding at least one acid to the mixture at pH less        than or equal to about 4.5 together with at least one monovalent        inorganic salt to retain surfactants from the latex/carbon        nanotube fiber concentrate.    -   27. The method of claim 21 wherein the mixture or concentrate        has a divalent or multivalent metal ion content of less than        about 20,000 parts per million.    -   28. The method of claim 21 wherein the mixture or concentrate        has a divalent or multivalent metal ion content of less than        about 10,000 parts per million.    -   29. The method of claim 21 wherein the mixture or concentrate        has a divalent or multivalent metal ion content of less than        about 1,000 parts per million.    -   30. The method of claim 21 wherein the coagulation step (c) is        such that agglomerations of carbon nanotubes comprise less than        1 percent weight of the concentrate and wherein the carbon        nanotube agglomerates comprise more than 10 microns in diameter.    -   31. An individually dispersed carbon nanotube/rubber or carbon        nanotube/elastomer concentrate comprising free flowing particles        wherein the concentrate contains a concentration of less than        20,000 parts per million divalent or multivalent metal salt.    -   32. An individually dispersed carbon nanotube/rubber or carbon        nanotube/elastomer concentrate comprising free flowing particles        wherein the concentrate contains agglomerations of carbon        nanotubes that comprise less than 1 percent by weight of the        concentrate and wherein the carbon nanotube agglomerates        comprise more than 10 micrometers in diameter.    -   33. A composite comprising the concentrate of claim 31 or 32.    -   34. A method of dispersing the individually dispersed carbon        nanotube/rubber or carbon nanotube/elastomer concentrate into an        elastomer by first melt mixing the elastomer and concentrate to        a uniform consistency before addition of other fillers and oils.    -   35. The composition of claim 5 comprising a mixture of natural        and synthetic elastomers such that each elastomer is compatible        with at least one of the elastomers such that the nanotubes are        individually dispersed in the mixture of elastomer(s).    -   36. The composition of claim 35 wherein at least one of the        elastomers does not comprise nanotubes.    -   37. A composition comprising one first elastomer and nanotubes,        another different second elastomer and nanotubes, and yet        another third elastomer which does not comprise nanotubes.    -   38. A process to increase cure rate of a composition comprising        at least one natural or synthetic elastomer and carbon        nanotubes, comprising selecting discrete carbon nanotubes to        form the cured composition, wherein the cured composition has at        least a 25 percent curing rate increase over the curing rate        obtained for a cured elastomer not comprising carbon nanotubes.    -   39. A composition of (A) elastomers, fillers and discrete carbon        nanotubes wherein to maintain or increase stiffness or hardness        as compared to (B) a composition not containing discrete carbon        nanotubes, wherein composition (A) has less filler content than        (B).    -   40. A composition of claim 39 wherein 1x parts per hundred        elastomer discrete carbon nanotube of composition (A) replaces        5x parts per hundred elastomer or more of the non-carbon        nanotube filler of composition (B), where x is 0.1-15.    -   41. A method of mixing carbon nanotubes and at least one first        elastomer, wherein a master batch of carbon nanotubes is first        melt mixed with the elastomer, either the same or different from        the first elastomer, at a temperature from about 20 to about        200° C., subsequently then additional elastomers, fillers, and        additives are added and melt mixed further, to produce a        composition suitable for vulcanization.    -   42. A method of mixing carbon nanotubes and at least one first        elastomer, wherein a master batch of carbon nanotubes is first        mixed with the elastomer, either the same or different from the        first elastomer, at a temperature from about 20 to about 200° C.        and in the presence of at least one solvent, then the at least        one solvent is removed, subsequently and optionally additional        elastomers, fillers and additives are added and mixed further to        produce a composition suitable for vulcanization.    -   41. A method of mixing carbon nanotubes and at least one first        elastomer, wherein a master batch of carbon nanotubes is first        mixed with the elastomer, either the same or different from the        first elastomer, at a temperature from about 20 to about 200° C.        and in the presence of at least one solvent, subsequently and        optionally additional elastomers, fillers and additives are        added and mixed further, followed by solvent removal to produce        a composition suitable for vulcanization.

We claim:
 1. A composition comprising an elastomer and a plurality ofoxidized, discrete carbon nanotubes, wherein the discrete carbonnanotubes have an aspect ratio of 25 or more, are multiwall, and arepresent in the range of from about 1 to about 30% by weight based on thetotal weight of the composition.
 2. The composition of claim 1 whereinat least 70 percent by weight of the nanotubes are discrete.
 3. Thecomposition of claim 1 wherein at least 80 percent by weight of thenanotubes are discrete.
 4. The composition of claim 1 in the form offree flowing particles.
 5. The composition of claim 1 wherein theoxidized, discrete carbon nanotubes comprise an oxidation speciesselected from carboxylic acid or derivative carbonyl containing species.6. The composition of claim 5 wherein the derivative carbonyl species isselected from ketones, quaternary amines, amides, esters, acyl halogens,and monovalent metal salts.
 7. The composition of claim 1 wherein theelastomer is a natural or synthetic elastomer.
 8. The composition ofclaim 1 wherein the elastomer is selected from the group consisting ofnatural rubbers, polyisobutylene, polybutadiene and styrene-butadiene,butyl rubber, polyisoprene, ethylene propylene diene rubbers andhydrogenated and non-hydrogenated nitrile rubbers, polyurethanes,polyethers, silicones, halogen modified elastomers, chloroprene,fluoroelastomers, and combinations thereof.
 9. The composition of claim1 which further comprises at least one filler.
 10. The composition ofclaim 1 which further comprises at least one surfactant or dispersingaid.
 11. The composition of claim 1 wherein the discrete carbonnanotubes are functionalized via covalent bonding, ionic bonding,chemisorption, intercalation, surfactant interactions, polymer wrapping,cutting, solvation, or a combination thereof.
 12. The composition ofclaim 1 further comprising carbon black, silica, graphene, oil, orantioxidant.
 13. The composition of claim 1 wherein the plurality ofoxidized, discrete carbon nanotubes comprise a residual metalconcentration of less than about 1000 parts per million as determined byenergy dispersive X-ray analysis.
 14. The composition of claim 1 in theform of a dispersion.
 15. A dispersion comprising: a plurality ofoxidized, discrete carbon nanotubes, wherein the discrete carbonnanotubes have an aspect ratio of 25 or more and are multiwall; and anelastomer selected from the group consisting of natural rubbers,polyisobutylene, polybutadiene and styrene-butadiene, butyl rubber,polyisoprene, ethylene propylene diene rubbers, hydrogenated andnon-hydrogenated nitrile rubbers, polyurethanes, polyethers, silicones,halogen modified elastomers, chloroprene, fluoroelastomers, andcombinations thereof.
 16. The dispersion of claim 15 wherein the UVabsorption at 500 nm is above 1.2 absorption units for a concentrationof 2.5×10⁻⁵ g CNT/ml.
 17. The composition of claim 15 wherein at least70 percent by weight of the total nanotubes in the dispersion arediscrete.
 18. The composition of claim 15 which further comprises water.19. The composition of claim 15 which further comprises at least onesurfactant or dispersing aid.